Ester-functional polysiloxanes and copolymers made therefrom

ABSTRACT

There is described a polysiloxane having the structure: 
                         
wherein R 1 , R 2 , and R 3  are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical, R 4  is independently a direct bond or hydrocarbon radical optionally substituted with oxygen and nitrogen, R 5  is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group, R 6  is independently a hydroxyl group, an amine group, an acid chloride group, or a sulfonyl halide group, x is from 1 to 300; y is from 0 to 50; and z is from 0 to 50. The polysiloxane is used to make various copolymers and polymer blends. A variety of articles can be made using the polysiloxane described as a polymer blend or copolymer.

BACKGROUND

Field of the Invention

The invention is directed to ester-functional polysiloxanes andcopolymers made therefrom.

Background of the Invention

Polycarbonate resins are well-known thermoplastic resins which have longbeen used in a variety of applications requiring resistance to impact.At low temperatures, generally lower than 20° C., polycarbonate becomesbrittle and its utility is thus limited by this shortcoming. It is knownthat the low temperature impact strength of polycarbonate may beimproved upon by the introduction (by copolymerization) of siliconeblocks into the carbonate structure. U.S. Pat. Nos. 3,189,662;3,419,634; 4,123,588; 4,569,970; 4,920,183 and 5,068,302 are noted todisclose relevant copolymers.

Relevant copolymers have been prepared in accordance with a meltblending process disclosed in U.S. Pat. No. 4,994,532. The processentails melt blending an aromatic polycarbonate resin and apolydiorganosiloxane having at least one functional carboxylic acidgroup.

Also relevant in the present context is U.S. Pat. No. 3,189,662 whichdisclosed a preparation method of polycarbonate siloxane co-monomerwherein the bisphenol moieties are bound to both the ends ofpolydimethylsiloxane. However hydrolysis of the siloxane monomer islikely to occur after polymerization due the presence of unstablesilicone-oxygen bonds connecting Si atom and reactive moieties. Thepresence of hydrolytically unstable Si—O—C bonds leads to poor weatherresistance and poor mechanical properties of the copolymer. While theforegoing silicone copolymers readily enter into a modification reactionbecause their hydroxyl groups are located at the para-position of thephenyl group, the polycarbonate resins produced are unstable and subjectto hydrolysis because of the presence of Si—O—C linkage in the polymerchain. Such problems have been solved by developing siloxane monomerscomprising of Si—C bonds which provides improved hydrolysis resistance.Monomers with improved heat stability and hydrolysis resistance havingsilicon alkyl bonds have been developed.

Three general paths to linear hydroxyaryloxy-terminated siloxanes of thefollowing general structure are known in the prior art:

(A) U.S. Pat. No. 3,189,662 describes the reaction of chloroterminatedpolysiloxanes with bisphenolic compounds eliminating hydrochloric acidas the byproduct; (B) U.S. Pat. No. 4,732,949 describes the reaction ofbisphenolic compounds with α,ω-bisacyloxypolydiorganosiloxanes in asolvent, and (C) U.S. Pat. No. 6,258,968 describes the reaction ofbisphenolic compounds such as hydroquinone with a cyclic dialkylsiloxane such as octamethylcyclotetrasiloxane in a solvent, whereby anacid catalyst is used and water is removed from the reaction mixture bydistillation.

As an alternative to hydroxyaryloxy-terminated siloxanes,carbonate-terminated siloxanes have also been used to preparepolysiloxane-polycarbonate block copolymers. For example, U.S. Pat. No.5,504,177 describes a solvent-free melt process for preparingpolydiorganosiloxane-polycarbonate block copolymers using Si—O—C freecarbonate-terminated siloxanes of the general formula:

However, this path has the disadvantage that it requires the use ofexpensive p-allylphenolic precursors for the group R³ and the use ofplatinum catalysts, which adds to the cost of the process.

U.S. Pat. No. 4,895,965 describes a method for making carboxy arylterminated organosiloxanes such as 1,1,3,3-tetramethyl-1,3-disiloxanediallylbis(benzoic acid) of general formula:

which is used for making polycarbonate-polysiloxane andpolyester-siloxane copolymers.

U.S. Pat. No. 4,879,378 discloses polysiloxane containing stericallyhindered phenol moieties, represented by general formula MD_(x)D′_(y)M,wherein

The sterically hindered phenol group attached to silicone atom viacarbonyloxy containing linkage. This type of materials is used asstabilizers for polymers.

U.S. Pat. No. 5,292,850 discloses polymeric stabilizers withpolysiloxane structure contain sterically hindered phenol groups andreactive groups capable of binding themselves to the polymer structureto be stabilized. These polymeric stabilizers are particularly suitablefor applications which require the no extractability of additives due tosolvents facts or soaps.

U.S. Pat. No. 8,426,532 describes the method of forming polycarbonategraft copolymers. Polycarbonate polymer or copolymer containing allylgroups provides the backbone for the graft copolymer, and pendant chainsare attached to the copolymer through allyl groups.

However, polycarbonate-polysiloxanes disclosed in the prior art have thedisadvantage that the precursor ester-functional polyorganosiloxanespossess non-suitable reactive terminal groups for interfacialpolymerization. Additionally, the prior art manufacture ofester-functional polysiloxane requires the use of expensive precursors.

Accordingly, there is a need for cost effective novel polysiloxanecopolymer compositions and polysiloxane polymer blends having anester-functional polysiloxane precursor with suitable terminal reactivegroup for interfacial copolymerization. There is a need for esterfunctional hydroxyl aryl terminated siloxane compositions with improvedthermal and hydrolytic stability. The present invention provides a costeffective method for producing ester-functional polysiloxanes. Theseester-functional polysiloxanes when used in copolymers or polymer blendsenhance low temperature impact resistance, flame resistance, hydrolyticand heat aging properties of the copolymers or polymer blends.

SUMMARY

Disclosed herein is a polysiloxane having the structure of Formula I:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical. R₄ is independently a direct bond or hydrocarbon radicaloptionally substituted with oxygen and nitrogen, R₅ is independently ahydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms,an aromatic group having 6 to 8 carbon atoms, an alkoxy group havingfrom 1 to 6 carbon atoms, or an aryloxy group, R₆ is independently ahydroxyl group, an amine group, an acid chloride group, or a sulfonylhalide group. x is from 1 to 300; y is from 0 to 50 and z is from 0 to50.

There is provided a copolymer composition having at least onepolyorganosiloxane having units of Formula II:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical; R₄ is independently a direct bond or dirhydrocarbon radicaloptionally substituted with oxygen and nitrogen; R₅ is independently ahydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms,an aromatic group having 6 to 8 carbon atoms, an alkoxy group havingfrom 1 to 6 carbon atoms, or an aryloxy group; wherein x ranges from 1to 300; y ranges from 0 to 50; and z ranges from 0 to 50.

Disclosed herein is a method of preparing a polysiloxane copolymer,including polymerizing a polyorganosiloxane of Formula I represented by:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical; R₄ is independently a direct bond or hydrocarbon radicaloptionally substituted with oxygen and nitrogen; R₅ is independently ahydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms,an aromatic group having 6 to 8 carbon atoms, an alkoxy group havingfrom 1 to 6 carbon atoms, or an aryloxy group; and R₆ is independently ahydroxyl group, an amine group, an acid chloride group, or a sulfonylhalide group; wherein x ranges from 1 to 300; y ranges from 0 to 50; zranges from 0 to 50 with a compound represented by:

where R₈ is independently a hydrogen, a halogen, an aliphatic grouphaving from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbonatoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxygroup; and R₉ is independently a hydroxyl group, an amine group, an acidchloride group, or a sulfonyl halide group; and V is selected from thegroup consisting of:

wherein R₁₀, R₁₁ are independently a hydrogen, halogen, an alkyl grouphaving from 1 to 18 carbon atoms, an aryl group having from 3 to 14carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, anaralkyl group having from 7 to 20 carbon atoms, an alkoxy group havingfrom 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbonatoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenylgroup having from 2 to 10 carbon atoms, an aralkyloxy group, a nitrogroup, an aldehyde group, a cyano group, or a carboxyl group in thepresence of a carbonate precursor, to provide the polysiloxanecopolymer.

DETAILED DESCRIPTION

Disclosed herein is an ester-functional polysiloxane,polysiloxane-copolymers and polysiloxane polymer blends preparedthereof. These copolymers and polymer blends exhibit advantageousproperties such as improved low temperature properties, improvedrheological properties during molding, improved chemical and scratchresistance, improved electrical insulation, improved heat aging andhydrolytic resistance properties.

In an embodiment, the invention herein is directed to a polysiloxanehaving the structure below:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical, R₄ is independently a direct bond or hydrocarbon radicaloptionally substituted with oxygen and nitrogen, R₅ is independently ahydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms,an aromatic group having 6 to 8 carbon atoms, an alkoxy group havingfrom 1 to 6 carbon atoms, or an aryloxy group, R₆ is independently ahydroxyl group, an amine group, an acid chloride group, or a sulfonylhalide group, x is from 1 to 300; y is from 0 to 50 and z is from 0 to50. The disclosure is also directed to polymer blends including thepolysiloxane described above.

There is described a method of preparing a polysiloxane compound of thestructure shown above. The method includes obtaining a hydrideterminated siloxane from cyclic oligomers, e.g. a cyclic siloxane. Thehydride terminated siloxanes can be obtained through ring openingpolymerization of a cyclic siloxane with disiloxane hydride in presenceof acidic and/or basic catalyst. The hydride terminated siloxanerepresented by the formula:

wherein R₁, R₂ and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical; wherein x is from 1 to 300; y is from 0 to 50; and z is from 0to 50, is reacted with allyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoateor allyl 2-(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)acetate or similarcompounds and their derivatives at an effective temperature of about 80to 200° C., preferably 100 to 150° C. and more preferably 80 to 100° C.to form a phenol-protected siloxane. Theallyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate or allyl2-(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)acetate and similar compoundsand their derivatives are “phenol-protected.” Tetrahydropyranyl (THP)ether is the group used for protection of the phenol. Phenol protectionis obtained for allyl-4-hydroxy benzoate, allyl-4-hydroxy phenyl acetateor similar compounds and their derivatives using tetrahydropyranyl (THP)ether in the presence of strong bases, Grignard reagents, hydrides,redox reagents, alkylating and acylating agents, and hydrogenationcatalysts. Allyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate or allyl2-(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)acetate and similar compoundsand their derivatives are tetrahydropyranylated and therefore“phenol-protected.” The phenol-protected siloxane compound is“deprotected” by using the mixture of polar solvents and a mineral acid,for example, THF/HCl to obtain phenol-deprotected siloxane. Variousother methods of phenol protection and de-protection which are presentlyunforeseen or unanticipated alternatives, modifications, variations, orimprovements therein may be subsequently made by those skilled in theart which are also encompassed by the claims of this invention. Thedeprotected siloxane is purified to remove organics. The purification isconducted at a reduced pressure at a temperature of about 150 to 300° C.to obtain the pure polysiloxane compound.

The invention is also directed to a copolymer composition having unitsincluding an ester-functional polysiloxane referred to as Formula I:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical; R₄ is independently a direct bond or hydrocarbon radicaloptionally substituted with oxygen and nitrogen; R₅ is independently ahydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms,an aromatic group having 6 to 8 carbon atoms, an alkoxy group havingfrom 1 to 6 carbon atoms, or an aryloxy group; wherein x ranges from 1to 300; y ranges from 0 to 50; and z ranges from 0 to 50.

In embodiments, Formula I is combined with a polycarbonate homopolymer,a polycarbonate copolymer, a polycarbonate-polyester, a polyester, apolysulfone, a polyethersulfone, a polyetheretherketone, a polyimide, apolyetherimide or combinations thereof to form a copolymer compositionor polymer blend.

In embodiments, the invention is also directed to a composition,including polysiloxane of Formula I or a copolymer including the unitsof Formula II and Formula III below.

wherein each R₇ is a hydrocarbon radical having 1 to 60 carbon atoms, adivalent hydrocarbon group, or a group derived from the structural unit;

where R₈ is independently a hydrogen, a halogen, an aliphatic grouphaving from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbonatoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxygroup; and R₉ is independently a hydroxyl group, an amine group, an acidchloride group, or a sulfonyl halide group; and V is selected from thegroup consisting of:

wherein R₁₀ and R₁₁ are independently a hydrogen, halogen, an alkylgroup having from 1 to 18 carbon atoms, an aryl group having from 3 to14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, anaralkyl group having from 7 to 20 carbon atoms, an alkoxy group havingfrom 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbonatoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenylgroup having from 2 to 10 carbon atoms, an aralkyloxy group, a nitrogroup, an aldehyde group, a cyano group, or a carboxyl group.

In embodiments of the copolymer disclosed above R₉ is a hydroxy groupand R₁₀ is alkyl group of from 1 to 6 carbon atoms.

The copolymer of the present invention may be prepared by polymerizing adihydroxy benzene compound with a bis-functionalized polyorganosiloxanecompound in the presence of a carbonate precursor, such as phosgene. Inone embodiment, the dihydroxy benzene compound is bisphenol A, and thebis-functionalized polydiorganosiloxane compound of Formula I.

In embodiments of the method of polymerizing the copolymer disclosedherein, the carbonate precursor is selected from the group consisting ofphosgene, diphosgene and diarylcarbonates, bis(methylsalicyl)carbonate,or combinations thereof.

In embodiments, the polymerization reaction is an interfacialpolymerization process conducted in the presence of a solvent andoptionally one or more catalysts.

In embodiments, the polymerization reaction is an interfacialpolymerization process conducted in the presence of a solvent thatincludes chlorinated aliphatic organic liquid, methylene chloride,chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane,tetrachloroethane, dichloropropane, 1,2-dichloroethylene, chlorobenzene,dichlorobenzene, chlorine-containing aromatic solvents, toluene, variouschlorotoluenes and the like, aqueous solvents such as de-ionized waterand optionally one or more catalysts.

In embodiments, the polymerization reaction is an interfacialpolymerization process conducted in the presence of a solvent, acaustic, and optionally one or more catalysts. When the carbonateprecursor is phosgene, diphosgene and diarylcarbonates,bis(methylsalicyl)carbonate, or a combination thereof, suitablecatalysts for the interfacial polymerization reaction includes aliphaticamines such as tertiary amine catalysts, trialkylamine; phase transfercatalyst such as catalysts of the formula (A₃)4L+B, wherein each A isindependently a C1-10 alkyl group; L is a nitrogen or phosphorus atom;and B is a halogen atom or a C1-8 alkoxy group or C6-18 aryloxy group.Combinations of such catalysts are also effective.

A variety of articles of manufacture can be made using the copolymers ofthe invention, and particularly using polymer blend compositionscontaining the copolymers of the invention (for example, in combinationwith a polycarbonate homopolymer). For example, such articles includebut are not limited to mobile phone housings, frozen food serviceequipment, personal safety applications including helmets, automotiveand motorcycle windshields, automotive sunroofs, other automotiveapplications including dashboards allowing for robust airbag deploymentwithout fragmenting, and automotive headlamp or electronics screenapplications, where clarity, flame retardance, and impact resistance arebeneficial.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and not limited to the materials,conditions, or process parameters set forth in these embodiments. Allparts are percentages by solid weight unless otherwise indicated.

EXAMPLES Example 1 Synthesis of Hydride Terminated Siloxane Fluid^(H)MD₄₅M^(H)

A mixture of octamethylcyclotetrasiloxane (D4) (500 g), and PuroliteCT275 (2.298 g) were placed in a 500 ml RB flask equipped with amagnetic stirrer, a reflux condenser and stirred under nitrogen. To thestirred mixture, 1,1,3,3-tetramethyldisioloxane (HMMH)(19.68 g) wasadded at room temperature. The flask heated and held at about 50° C. forabout one hour and then the temperature was increased to about 60° C.for about one hour. The temperature was then increased to 70° C. forabout 2 hours and then increased to about 80° C. for about 4 hours.After completion of the reaction, the flask was cooled to less than 30°C., treated with Celite (0.750 g) and filtered. Volatiles were removedby applying a vacuum at 130° C./5 mbar to yield 480 g of clear colorlessliquid. The liquid had the following characteristics: Solid content was98%, Viscosity was 15-20 mPas, Hydride content was 11.68 cc H₂/g (0.0521wt %), the Molecular weight Mn was 4648, and the polydispersity index(PDI) was 1.6.

Example 2 Synthesis of phenol (allyl-4-hydroxy-benzoate) TerminatedSiloxane Fluid ^(AHB)MD₄₅M^(AHB)

A 250 ml RB flask was charged with ^(H)MD₄₅M^(H) (75 g, as preparedabove) and alumina supported platinum catalyst (0.350 g) was stirredunder notrogen and brought to 80° C.Allyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate (3,4-dihydro-2H-pyranprotected phenol) (9.622 g) was charged into an addition funnel andadded drop wise to maintain a reaction temperature less than about 100°C. Following the addition, the reaction mixture was brought to about 80°C. for 1 hour and then the temperature was increase to about 100° C. forabout 2 hours. Completion of the hydrosilylation reaction was confirmedby proton NMR. The reaction mixture was allowed to cool to less than 30°C., treated with Celite (0.5 g) and filtered. Deprotection of phenol isdone using THF/HCl mixture at 30° C. The resulting fluid was thenstripped at 200° C./5 mbar to yield clear pale yellow liquid. The liquidhad the following characteristics: Solid content was 98%, Viscosity was130-150 mPas, the Molecular weight Mn was 4653, and the PDI was 1.8.

Example 3 Synthesis of phenol (allyl-4-hydroxyphenyl acetate) TerminatedSiloxane Fluid ^(AHP)AMD₄₅M^(AHPA)

Using the same reaction conditions in Example 1, allyl2-(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)acetate((3,4-dihydro-2H-pyranprotected phenol allyl-4-hydroxyphenyl acetate) was used in the place ofAllyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate (3,4-dihydro-2H-pyranprotected phenol). The liquid had the following characteristics: Solidcontent was 98%, Viscosity was 127-140 mPas, the Molecular weight Mn was4703, and the PDI was 1.7.

Example 4 Synthesis of Phenyl Containing Siloxane Fluid^(H)MD_(61.87)D^(Ph) _(25.99)M^(H)

A 1 L 3-necked round flask equipped with a mechanical stirrer, athermometer and a vacuum distillation was charged 352 g of silanolterminated methyl phenyl siloxane fluid (YF3804), 149 g of hydrogenterminated methyl siloxane fluid (M′D₁₈M′) and 81.5 g ofoctamethylcyclotetrasiloxane. The mixture was heated to 90° C. and thenadded linear phosphonitrilic chloride (LPNC) catalyst for condensationand rearrangement reactions. The mixture was vacuumed to 90 mmHg andheld at about 90° C. for 20 hours. The reaction mixture was then added15.3 g of sodium hydrogen carbonate to neutralize the LPNC catalyst. Themixture was cooled to less than about 40° C. and filtered with Celite.The refractive index of each sample was measured. The solid content was98 percent.

Example 5 Synthesis of phenol (allyl-4-hydroxy-benzoate) TerminatedSiloxane Fluid ^(AHB)MD_(61.87)D^(Ph) _(25.99)M^(AHB)

A 250 ml RB flask was charged with ^(H)MD_(61.87)D^(Ph) _(25.99)M^(H)(50 g, as prepared above) and alumina supported platinum catalyst (0.290g) stirred under nitrogen and brought to about 80° C.Allyl-4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate (3,4-dihydro-2H-pyranprotected phenol) (2.7 g) was charged into an addition funnel and addeddrop wise at a rate to maintain a reaction temperature to less thanabout 100° C. Following the addition the reaction mixture was brought toabout 80° C. for 1 hour and then the temperature was increased to about100° C. for 2 hours. Completion of the hydrosilylation reaction wasconfirmed by proton NMR. The reaction mixture was allowed to cool toless than 30° C., treated with Celite (0.5 g) and filtered. Deprotectionof phenol is done using THF/HCl mixture at 30° C. The resulting fluidwas then stripped at 200° C./5 mbar to yield clear pale yellow liquid.The liquid had the following characteristics: Solid content was 98%,Viscosity was 350-360 mPas, the Molecular weight Mn was 4114, and thePDI was 2.2.

Example 6 Synthesis of phenol (allyl-4-hydroxy-benzoate) terminatedsiloxae fluid ^(AHB)MD_(x)D^(vinyl)M^(AHB)

A 250 ml RB flask was charged with ^(AHB)MD₁₀M^(AHB) (20 g, as preparedabove), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (4.45g) (D4 vinyl) and concentrated sulfuric acid catalyst (0.022 mg). Thereaction mixture was brought to about 80° C. and stirred under nitrogenfor 16 hours. After completion of the reaction the reaction mixture wasneutralized by adding solid sodium carbonate and filtered throughCelite. The resulting fluid was then stripped at 190° C./5 mbar to yieldclear pale yellow liquid. The liquid had a solid content of 98%.

Comparative Example 1 Synthesis of phenol (Eugenol) terminated siloxanefluid ^(Eu)MD₄₅M^(Eu)

A 250 ml RB flask was charged with ^(H)MD₄₅M^(H) (50 g, as preparedabove) and alumina supported platinum catalyst (0.290 g) and stirredunder nitrogen and brought to 80° C. Allyl-3methoxy-4-hydroxybenzoate(Eugenol) (9.622 g) was charged into an addition funnel and added dropwise at a rate to maintain a reaction temperature at less than about100° C. Following the addition the reaction mixture was brought to 80°C. for 1 hour and then the temperature was increased to 100° C. for 2hours. Completion of the hydrosilylation reaction was confirmed byproton NMR. The reaction mixture was allowed to cool to less than 30°C., treated with Celite (0.5 g) and filtered. The resulting fluid wasthen stripped at 200° C./5 mbar to yield clear pale yellow liquid. Theresulting fluid was then stripped at 200° C./5 mbar to yield clear paleyellow liquid. The liquid had the following characteristics: Solidcontent was 98%, Viscosity was 135 mPas, the Molecular weight Mn was5700, and the PDI was 2.05.

Example 7 Synthesis of Polycarbonate-Polysiloxane Copolymers

10.278 g of Bisphenol-A, 1.142 g of phenol terminated siloxane fluid and0.113 g of benezene triethylammonium chloride (BTAC) were added to thefour necked RB flask containing 50 mL each of water and dichloromethane(DCM). 7.42 g of triphosgene was weighed in a glass vial under nitrogenatmosphere and was dissolved in 25 mL DCM and transferred to theaddition funnel carefully. 25 mL of 25-30 wt % NaOH solution wastransferred to second additional funnel fixed in the reactor. Bothtriphosgene and NaOH are added to the reaction mixture simultaneouslywith vigorous stirring (300-400 rpm). NaOH addition was carefully donein such a way that pH of the reaction mixture was maintained between 5and 6. The stirring was continued for another 20 min. The remainingamount of NaOH was added to increase the pH to 10-11. The reactionmixture was stirred for another 5-10 minutes, 0.16 g of 4-cumyl phenol(pCP) and 54.4 mg of triethyl amine (TEA) were added. Stirring wascontinued for another 5-10 minutes and the pH was increased to 12 byadding aqueous NaOH. The reaction was stopped and organic layer wasseparated from aqueous layer using separating funnel. The polymer(organic layer) was washed with 1N HCl and precipitated in large excessof methanol. The final product was dried in an oven at about 60 to about70° C. overnight. Similar procedures were repeated using differentphenol terminated siloxane fluid in examples and comparative examples.

TABLE 1 Compositional details of PC—Polysiloxane copolymers SamplesM_(n,) sec M_(w,) sec PDI Copolymer I: PC-Siloxane (Example-2) 4096572377 1.7 copolymer Copolymer II: PC-Siloxane (Example-3) 37731 577311.5 copolymer Copolymer III: PC-Siloxane (Example-5) 27376 43612 1.5copolymer Copolymer IV: PC-Siloxane (Comparative 42974 64852 1.5example 1) copolymer

As shown in Table 1 above, the polysiloxane-polycarbonate copolymersprepared by using ester-functional polysiloxane of Examples 2, 3 and 5showed generally comparable number average molecular weight (Mn), weightaverage molecular weight (Mw) and polydispersity index (PDI) as comparedwith those of the polysiloxane-polycarbonate copolymers preparedaccording to the Comparative Example 1 (Eugenol terminatedpolysiloxane-polycarbonate copolymer). This clearly indicates thepolymerizability of ester-functional polysiloxane and functionalizedester-functional polysiloxane with bisphenol-A in presence oftri-phosgene is quite similar to standard eugenol terminal polysiloxane.In addition, the cost effective ester-functional polysiloxane materialswould copolymerized with other monomers to form the correspondingcopolymers with distinguishable properties improvement.

Preparation of Polycarbonate and Polycarbonate-Polysiloxane blends: Upto 5 wt % of the polycarbonate-polysiloxane copolymers (Copolymers I toIV) made are melt-blended in Haake batch mixer with approximately 95 wt% of polycarbonate at 305° C. for 7 min. Compositional details are shownin below Table 2. The molten strands were collected and used samplepreparation for flammability tests.

TABLE 2 Polycarbonate- Polycarbonate- Polysiloxane polysiloxanecopolymer in copolymer content Blends the blend (wt %) in the blendBlend-1 Copolymer I 5 Blend-2 Copolymer II 5 Blend-3 Copolymer III 5Polycarbonate — — Homopolymer

In another embodiment, the thermoplastic composition includes about 40to about 80 wt. % of the polycarbonate resin; more than 5 wt. % of thepolycarbonate-polysiloxane copolymer, Optionally, the composition maycomprise about 2 to about 15 wt. % of the impact modifier, 2 to 15 wt. %of an organic phosphorus containing flame retarding agent, e.g., about 8to 15 wt. %, based on the total combined weight of the composition,excluding any filler. These amounts provide optimal flame retardance,together with good notched Izod impact strength at ambient temperature;good notched Izod impact strength at low temperature; and/or good heatdeflection temperature. In addition, these amounts provide compositionsthat meet UL94 5VB, VON1 test requirements and that meet other criteriasuch as minimum time to drip, as described herein. Relative amounts ofeach component and their respective composition may be determined bymethods known to those of ordinary skill in the art.

Flammablity Tests

In one embodiment, the thermoplastic compositions are of particularutility in the manufacture flame retardant articles that pass the UL94vertical burn tests. In the UL94 vertical burn test, a flame is appliedto a vertically fastened test specimen placed above a cotton wool pad.Flammability tests were performed following the procedure ofUnderwriter's Laboratory Bulletin 94 entitled “Tests for Flammability ofPlastic Materials, UL94.” According to this procedure, materials may beclassified as HB, V0, UL94 V1, V2, 5VA and/or 5VB on the basis of thetest results obtained for five samples as per the following relatedcriteria (Table 3).

TABLE 3 Flammability test results criteria conditions: CriteriaConditions V-0 V-1 V-2 Afterflame time for each individual ≦10 s ≦30 s≦30 s specimen t1 or t2 Total afterflame time for any ≦50 s ≦250 s  ≦250s  condition set (t1 plus t2 for the 5 specimens) Afterflame plusafterglow time for ≦30 s ≦60 s ≦60 s each individual specimen after thesecond flame application (t2 + t3) Afterflame or afterglow of any No NoNo specimen up to the holding clamp Cotton indicator ignited by No NoYes flaming particles or drops

TABLE 4 Flammability Test results for Polycarbonate Homopolymer andPolycarbonate with Polycarbonate-Polysiloxane blends Specimens nominalthickness 4 mm Standard UL94 Av Av Blend (t1 + t2) s Remarks-1 (t2 + t3)s Remarks-2 Type Blend 1 7 Sample 9.3 Sample V0 didn't didn't drip dripBlend 2 28.6 Sample 49.3 Sample V1 didn't didn't drip drip Blend 3 16.3Sample 27.3 Sample V1 didn't didn't drip drip Polycarbonate 16 Sample21.3 Sample V2 Homopolymer didn't dripped drip particles, that ignitecotton

As shown in Table 4 above, the blend compositions (Blend 1, 2 and 3)prepared using the polycarbonate-ester-functional polysiloxanecopolymers (Copolymers I, II, III) respectively are generally havingbetter flame resistance than Polycarbonate Homopolymer. Considering theaverage flame out time after the lightings, the blend composition(blend 1) with the instant polycarbonate-ester functional polysiloxanecopolymer (Copolymer I) showed extremely improved flame resistance.Moreover, none of the instant copolymers incorporated blend compositionsshow dripped particles and cotton ignition.

Tensile Tests:

Tensile tests of dumb-bell shaped specimens were carried out using anInstron tensile tester using a 5 KN load cell. The gauge length of thedog-bone specimens was 0.97 inch and the cross-head speed was 0.2inch/min. The data were analyzed using Bluehill Lite software. Table 5describes the results obtained from the tensile tests.

TABLE 5 Tensile Test of Blends Young's Modulus Tensile Stress at TensileStrain at Blend Type (psi) Yield (psi) Break (%) Blend 1 136,032 ±11,909 10,078 ± 1,159 167 ± 10.8 Polycarbonate 129,977 ± 9,215   9,539 ±1,493 175 ± 7   HomopolymerTypically, the tensile strength measurements depicts that theincorporation of instant polycarbonate-polysiloxane copolymers ofinvention into the polycarbonate homopolymer (Blend 1) are maintainingthe polycarbonate material property without any decrement in materialproperty in spite of improving the other properties while addition.Low Temperature Impact Strength Tests:

In another embodiment the instant specimens were evaluated using notchedizod tests. The test procedure was based on the ISO 180/1A method. Theresults of the test were reported in terms of energy absorbed per unitof specimen width, and expressed in Izod Notch Energies (KJ/m2) and areshown in Table 6. Typically the final test result is calculated as theaverage of test results of five test bars.

TABLE 6 Izod Test of Blends Izod test Izod test Izod test Izod test Izodtest Blend Type at 23° C. at 0° C. at −20° C. at −40° C. at −60° C.Blend 1 72.21 27.81 23.1 17.7 13.2 Standard 11.88 0.32 1.69 1.67 0.91Deviation Poly- 68.08 18.07 16.18 12.87 9.93 carbonate Homo- polymerStandard 3.99 1.24 0.86 0.62 1.39 Deviation

As the Izod test temperature is lowered below room temperature, theenergy absorbed by instant polycarbonate-polysiloxane copolymersincorporated blends is significantly higher than the polycarbonatehomopolymer.

It will be appreciated that variants of the above-disclosed and otherfeatures and functions or alternatives thereof, may be combined intoother different systems or applications. Various presently unforeseen orunanticipated alternatives, modifications, variations, or improvementstherein may be subsequently made by those skilled in the art which arealso encompassed by the following claims.

What is claimed is:
 1. A polyorganosiloxane having the structure ofFormula I:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical, wherein at least one of R₁, R₂ and R₃ is selected from anunsaturated radical or an alkenyloxy radical; R₄ is independently adirect bond or hydrocarbon radical optionally substituted with oxygenand nitrogen; R₅ is independently a hydrogen, a halogen, an aliphaticgroup having from 1 to 6 carbon atoms, an aromatic group having 6 to 8carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or anaryloxy group; R₆ is independently a hydroxyl group, an amine group, anacid chloride group, or a sulfonyl halide group; and x is from 1 to 300;y is from 0 to 50; and z is from 0 to
 50. 2. A composition comprisingthe polyorganosiloxane of claim 1, and a polymer selected from the groupconsisting of: polycarbonate homopolymers, polycarbonate copolymers,polycarbonate-polyesters, polyesters, polysulfones, polyethersulfones,polyetheretherketones, polyimides and polyetherimides.
 3. An articlecomprising the composition of claim
 2. 4. The article of claim 3,wherein the article is selected from the group consisting of mobilephone housings, frozen food service equipment, helmets, automotivewindshields, motorcycle windshields, automotive sunroofs, dashboards,headlamps, and electric screens.
 5. A copolymer composition containing acopolymer comprising at least one polyorganosiloxane having units ofFormula III:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical, wherein at least one of R₁, R₂ and R₃ is selected from anunsaturated radical or an alkenyloxy radical; R₄ is independently adirect bond or hydrocarbon radical optionally substituted with oxygenand nitrogen; R₅ is independently a hydrogen, a halogen, an aliphaticgroup having from 1 to 6 carbon atoms, an aromatic group having 6 to 8carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or anaryloxy group; x is from 1 to 300; y is from 0 to 50; and z is from 0 to50.
 6. The copolymer composition of claim 5, wherein the copolymerfurther comprises structural units of Formula IV:

wherein each R₇ is a hydrocarbon radical having 1 to 60 carbon atoms, adivalent hydrocarbon group, a group derived from the structural unit ofFormula V

where R₈ is independently a hydrogen, a halogen, an aliphatic grouphaving from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbonatoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxygroup; and R₉ is independently a hydroxyl group, an amine group, an acidchloride group, or a sulfonyl halide group; and V is selected from thegroup consisting of:

wherein R₁₀, R₁₁ are independently a hydrogen, halogen, an alkyl grouphaving from 1 to 18 carbon atoms, an aryl group having from 3 to 14carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, anaralkyl group having from 7 to 20 carbon atoms, an alkoxy group havingfrom 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbonatoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenylgroup having from 2 to 10 carbon atoms, an aralkyloxy group, a nitrogroup, an aldehyde group, a cyano group, or a carboxyl group.
 7. Thecopolymer composition of claim 5, further comprising a polycarbonatehomopolymer, a polycarbonate copolymer, a polycarbonate-polyester, apolyester, a polysulfone, a polyethersulfone, a polyetheretherketone, apolyimide or a polyetherimide.
 8. An article comprising the copolymercomposition of claim
 5. 9. The copolymer composition of claim 6, whereinR₉ is a hydroxy group and R₁₀ is an alkyl group of from 1 to 6 carbonatoms.
 10. The article of claim 8, wherein the article is selected fromthe group consisting of mobile phone housings, frozen food serviceequipment, helmets, automotive windshields, motorcycle windshields,automotive sunroofs, dashboards, headlamps and electric screens.
 11. Amethod of making an article comprising: molding, shaping, or forming thecopolymer composition of claim 5 to form the article.
 12. A method ofpreparing a polysiloxane copolymer, comprising polymerizing apolyorganosiloxane of Formula I represented by:

wherein R₁, R₂, and R₃ are independently a hydrocarbon radical, anunsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxyradical, wherein at least one of R₁, R₂ and R₃ is selected from anunsaturated radical or an alkenyloxy radical; R₄ is independently adirect bond or hydrocarbon radical optionally substituted with oxygenand nitrogen; R₅ is independently a hydrogen, a halogen, an aliphaticgroup having from 1 to 6 carbon atoms, an aromatic group having 6 to 8carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or anaryloxy group; and R₆ is independently a hydroxyl group, an amine group,an acid chloride group, or a sulfonyl halide group; wherein x is from 1to 300; y is from 0 to 50; and z is from 0 to 50, with a compound ofFormula V represented by

where R₈ is independently a hydrogen, a halogen, an aliphatic grouphaving from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbonatoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxygroup; and R₉ is independently a hydroxyl group, an amine group, an acidchloride group, or a sulfonyl halide group; and V is selected from thegroup consisting of

wherein R₁₀, R₁₁ are independently a hydrogen, halogen, an alkyl grouphaving from 1 to 18 carbon atoms, an aryl group having from 3 to 14carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, anaralkyl group having from 7 to 20 carbon atoms, an alkoxy group havingfrom 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbonatoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenylgroup having from 2 to 10 carbon atoms, an aralkyloxy group, a nitrogroup, an aldehyde group, a cyano group, or a carboxyl group in thepresence of a carbonate precursor.
 13. The method of claim 12, whereinR₉ is a hydroxy group and R₁₀ is an alkyl group of from 1 to 6 carbonatoms.
 14. The method of claim 12, wherein the carbonate precursor isselected from the group consisting of phosgene, diphosgene,diarylcarbonate, bis(methylsalicyl)carbonate and a combination thereof.15. The method of claim 12, wherein the polymerizing is an interfacialpolymerization process conducted in the presence of a solvent andoptionally one or more catalysts.
 16. The method of claim 15, whereinthe one or more catalysts are selected from the group consisting of:aliphatic amines, trialkylamine; and phase transfer catalysts of theformula (A₃)₄L+B, wherein each A is independently a C1-10 alkyl group, Lis a nitrogen or a phosphorus atom; and B is a halogen atom, a C1-8alkoxy group or C6-18 aryloxy group.
 17. The method of claim 12, whereinthe polymerizing step is an interfacial polymerization process conductedin the presence of a solvent, a caustic, and optionally one or morecatalysts, and wherein the carbonate precursor is phosgene, diphosgene,diarylcarbonate, bis(methylsalicyl)carbonate, or a combination thereof.18. The method of claim 12, wherein polymerizing comprises reactingbisphenol A with phosgene in a biphasic solvent in the presence of aphase transfer catalyst to form a bischloroformate; wherein the methodfurther comprises adding polyorganosiloxane.
 19. The method of claim 18,wherein the bischloroformates of polyorganosiloxane are formed in a tubereactor, and then added into an interfacial polycondensation reactorwith catalyst.